Basic bismuth salts of aromatic mercury compounds



Patentecl Aug. i936 UNITED STATES PATENT OFFICE BASIC BISMUTH SALTS F AROMATIO MERCURY COMPOUNDS No Drawing. Application October 25, 1929, Se rial No. 402,542. In Germany December 3,

The present invention relates to bismuth salts of mercury compounds of the aromatic series substituted by one side chain or a heterocyclic nucleus and'containing at least one acid group, the mercury in said compounds being bound to a side chain or to the heterocyclic nucleus.

We have found that mercurycompounds of the aromatic series substituted by one side chain or a. heterocyclic nucleus and containing at least one acid group, the mercury in said compounds being bound to a side chain or to the heterocyclic nucleus, can easily be transformed into basic bismuth salts. The new compounds can be obvtained by causing a soluble salt of the mercury compounds to react with simple or complex bismuth salts. These new preparations are suitable for the depot treatment, for instance, of

syphilis.

In comparison with the known mercury salts of complex bismuthio acids, the new preparations have a considerably reduced toxicity and at least the same curative power. I Themercury which in the known salts is bound in a pure ionogen manner, is bound in the new salts to a side chain or the heterocyclic nucleus; whereby a reduction of the toxicity is caused. V

The following examples serve to illustrate our invention, but they are not intended to limit it thereto.

1. 52.3 grams of a compound of the following formula:

OCH:COONa prepared according to Example 40f U. S.Patent while well stirring. By the addition of 2N caustic soda solution the whole is neutralized and the white salt of the following probable formula:

is filtered by suction, washedwith water, alco hol and ether and dried in a vacuum.

2. In the same manner as indicated in Exampie 1, there can be obtained the basic bismuth 5 Claims. (Cl. 260-13) salt of the arsonic acid of the following probable formula:

NH-COCHa.

by causing 60 grams of the sodium salt of acom' pound of the following formula:

NH-CO OH:

dissolved in 180 cc. of water to react with a solution of 48.5 grams of bismuth nitrate.

The starting material can be obtained by causing 3 acetylamino-4-hydroxybenzene-l-arsonic acid to react with allyl bromide in an alkaline solution. The acid readily dissolves in methyl alcohol and crystallizes from water in the form of white needles. The mercurization is efiected in the same manner as in the starting material used in Example 1.

3. 39.5 grams of. the sodium salt of a compound of the following formula:

IIIH

prepared by causing inorganic mercury compoundsto act upon a compound of the following formula;

sOzHi are dissolved in times the quantity of water. Then a solution of 48.5 grams of bismuth nitrate in glycerine and water is introduced while well stirring. Thereby the basic bismuth salt of the arsonic acid of the following probable formula:

AsOaBiOH AsosBlQH separates in the form of a colorlgass precipitate, which is filtered by suction, washed with water and dried in a vacuum.

In order to prepare the starting material 3.4- diaminobenzene-arsonic acid is transformed'by interaction with potassium xanthogenate into a compound of the following formula:

As S 1H2 and the latter is convertedinto the correspond- ITIH I COOBiO COOBiO by causing 31.5 grams of the sodium salt of a compound of the following formula:

N H- c-s-n -sc NH coon coon i solved n: l5liter ofwa er. to eact: with a solution of 48.5 grams of bismuthnitrate.

' The ta, t n mat ria an e pr pared by causing inorganic mercury salts to ac tyupon a compound of the following formula:

COOH

which can be prepared according to Example 3 of 'UJ'S. 'PatentNo."'1,'558,584; dated October '27,

i 1925, in the nameof Max Bockmiihl'f'Giista'v Ehrhardt and Paul 'Fritas'ch'e.

5. The colorless bismuth salt of the following probable formula:

NH-CSHg-S.C

can be obtained in a manner analogous to that indicated in Example 3, by adding 48.5 grams of bismuth nitrate to 34.9 grams of the sodium salt of a compound of the following formula:

OaH SOaH dissolved in 500 cc. of water.

The starting material can be prepared by causing sodium xanthogenate to act upon 1,2-diaminobenzene-i-sulfonic acid (cf. Berichte der Deutschen Chemischen Gesellschaft, volume 21, page 3221). The product crystallizes from diluted alcohol in the form of beautiful, colorless laminae and, when mixed with inorganic mercury; salts' in an aqueous solution, the corresponding ir erc'ury derivative is obtained.

" 6. 33.6 grams of the sodium salt of meta-mercl y-allylthioureab enzoic acid of the following formula coon separates, which is filtered by suction, Washed with water and dried in a vacuum.

Instead'of the benzene-' and benzimidazolcompounds respectively, there can, of course, also be used as starting materials other aromatic cornpounds, as for instance naphthalene and oth'er heterocyclic compounds, as for instance oxazolderivatives or the like.

The nuclei ma'y be substituted by alkyls halogen, anunoand nitro groups or the like. Instead of thefacidradicals in the examples, there can also 'stand other acid 'radi'c'als, for in; stance insteadiof fthe oxy-acetic radical in Exampll 1, the" carboxylic acid, "sulfonic acid radical Iristeadof the mercury-allyl-compounds mentioned insExamples l and 2, there can also be used mercury compounds of crotonyl and higher homologous radicals.

We claim:

1. A basic bismuth salt of a compound of the C HL 2iQ. Q? Q. ntainin qne e ro a mercurycontaining aliphatic sme ma free mnian d roun- A sic v 1 2121 1. al er a emr nmleit q obtainable by causing a water-soluble bismuth salt to act upon a soluble salt of a compound of the following formula:

O-CH:COONa 4. The basic bismuth salt of the following formula:

OCHz-CH(OH)OH -Hg0CO-OH:

obtainable by causing a water-soluble bismuth salt to act upon a soluble salt of a compound of the following formula:

NIP-000E: 5

AsOsHa 5. The basic bismuth salt of the following for- 10 mula:

-OOOBiO obtainable by causing a water-soluble bismuth salt to act upon a soluble salt of a compound 20 of the following formula:

KARL STREITWOLF. ALFRED FEHRLE. PAUL FRITZSCHE. WALTER HERRMANN. 

